Acylamino derivatives of the anthrapyrimidine series



Patented May 19, 1936 PATENT OFFICE ACYLAMINO DERIVATIVES OF THE ANTHRAPYRIMIDINE SERIES Max Albert Kunz, Mannheim, and Karl Koeberle,

Ludwigshafen-on-the-Rhine, Germany,

signors to General Aniline Works, Inc., New York, N. Y., a corporation of Delaware No Drawing.

Application January 14, 1932,

Serial No. 586,692. In Germany January 21,

35 Claims.

The present invention relates to new compounds which are acylamino derivatives of the anthrapyrimidine series, and process of producing same.

We have found that anthrapyrimidines to which an organic radicle is attached by means of an acylamino, in particular a carboxylamino group, are valuable coloring matters, in particular vat dyestufis, and intermediate products for the preparation thereof and may also be used as pigments. The said anthrapyrimidine derivatives can be produced by condensation of an acylaminoanthraquinone containing a further nitrogen atom in an alpha position and convertible into anthrapyrimidines with compounds capable of forming the pyrimidine ring, for example acid amides, or ammonia in case acylaminoanthraquinone-1(N).2-oxazoles are employed as initial materials, whereby the pyrimidine ring is formed, or by acylation of aminoanthrapyrimidines, or by condensation of negatively substituted anthrapyrimidines with acid amides. They may further be prepared by condensing l-nitroanthraquinone carboxylic or sulphonic acids or halides thereof with amines, reducing the nitro group and condensing the reduction products with acid amides to form the pyrimidine ring. Several of the aforesaid methods may also be combined.

For example by heating 1-amino-5-benzoylaminoanthraquinone with formamide, 5-benzoylamino-1.9-anthrapyrimidine is obtained according to the following formula:--

5-benzoylamino-L9- l-amino-E-benzoylaminoanthrapynmidme.

anthraquinone.

ganic radicle, according to the following formulee:-

4-amino-L9 anthrapyrimidine 4-acylamino-L9- the following formulae:

H V H l I N N N N II H I l NH O HQN-COCQH3 O CsHl (Y being a halogen) As results from the aforedescribed methods of producing the new derivatives of anthrapyrimidine, most various kinds of initial materials may be used, for example amino-anthrapyrimidines, halogenanthrapyrimidines, u-aminoanthraquinones substituted by a further amino group or halogen and anitroanthraquinone carboxylic and sulphonic acids and substitution products thereof. When starting from aminoanthrapyrimidines or u-aminoanthraquinones containing a further amino group and subsequently form- 1 ing the pyrimidine ring, the new compounds are formed by condensation with organic acids whereby in case such acids of higher molecular weight are used, these are preferably employed in the form of their anhydrides or still better in the form of their halides, in particular chlorides. Halogenanthrapyrimidines or the corresponding a-aminohalogenanthraquinones, when used as starting materials, are to be condensed with the amides of the organic acids. In the following we will give a series of organic acids which either in the free state or in the form of their amides, an-

hydrides or halides have proved suitable for the purpose of ourinvention: aliphatic monoand 'poly-carboxylic acids, such as formid'acetic, chloracetic, butyric, propionic, valeric, palmitic, stearic,

. oxalic, molanic, succinic, adipic, suberic, pyroacemic, lactic, citric, maleic, oleic acids cycloali-' phatic acids, such as hexa-hydrobenzoic acid and naphth enic acids; aromatic carboxylic and sulphonic acids for example benzene .mono and polycarboxylicand sulphonic acids, such as benzoic, phthalic, isophthalic and terephthalic acids, the various monoand poly-carboxylic and sulphonic acids derived from naphthalene, anthracene, an-

thraquinone, fiuorene, fiuorenone, phenanthrene, benzanthrone, anthanthrone, the various dianthrones, ms-benzdianthrone, ms-naphthodianthrone, ms-anthradianthrone, the saidacids of the heterocyclic series, such as those derived from pyridine, quinoline, acridine, acridone, an thraquinone-benzacridone, anthraquinonethioxanthrone, pyrazolanthrone, anthrapyrimidone,

anthrapyridone, and pyrolanthrone. Substitution products of the aforesaid acids may be used as well, for example their alkyl, aryl and acyl derivatives, suchas toluic acids, xylene carboxylic acids, mesitylenic acid, cinnamic acid, hydrocinnamic acid, benzoyl-formic acid, b'enzoyl-acetic acid, acetyl-benzoic acid, diphenylcarboxylic acid, diphenylmethane carboxylic acid, benzophenone carboxylic acid, anthraquinonoyl-benzoic acid. Moreover, the halogen derivative of F the aforesaid acids, viz. their fluorine, chlorine,

bromine and iodine derivatives, the aforesaid acids when substituted bynitro, hydroxy, alkoxy,

aryloxy' or amino groups or amino groups in which the hydrogen atoms are replaced by organic radicles, such asalkyl, aryl or acyl groups, may be used. Further, there may be used acids of the aforedescribed kind when substituted by cyano, thiocyano, mercapto or substituted mercapto groups, viz. the thiocyanates. and thioethers, or acids containing a further carboxylic group-which is esterified or in which the hydroxy group is replaced by the amino group. When.

it is intended to produce compounds of the kind described in'which the acyl groupis attached to the anthrapyrimidine nucleus which as stated above are preferably prepared by condensing an u-nitroanthraquinone carboxylic or sulphonic acid chloride with amines, reducing the nitro tion of the new compounds, may contain any of the substituents. which as stated above may be presentin the acid'component, also connected to the Py-C atom, in particular halogen, alkyl, aryl, 'aralkyl, amino, substituted amino, hydroxy, alkoxy, nitro and cyano groups. 'In ad: dition to the said substituents the 2-position in the anthrapyrimidine may be substituted by a 2'-anthrapyrimidine'radical. That is to say the invention includes the production of acylamino compounds of 2-2'-dianthrapyrimid'yls which latter 'productsare obtainable by alkaline con- 2,o4o,s57 densation of anthrapyrimidines. As substituents in the Py-C position, alkyl, aryl, aralkyl, amino, substituted amino, alkoxy and aryloxy groups and in particular halogen are valuable.

The aforesaid anthrapyrimidines substituted on the Py-C atom by organic radicles maybe produced by employing another acid amide than formamide, for example acetic amide, for the condensation with an alpha-aminoanthraquinone. It is, however, more suitable to produce these substituted anthrapyrimidines from the corresponding anthraquinone-l (N) .2-oxazoles by heating them with ammonia under pressure. 'A further convenient method for producing these substituted anthrapyrimidines consists in starting from anthrapyrimidones which may already contain an acylamino, amino, nitro, alkyl, alkoxy, aryloxy group or a halogen atom in the anthraquinone nucleus, with agents capable of replacing oxygen or hydroxy groups by halogen, such as the halides of phosphorus or sulphur, for example phosphorus pentachloride, tribromide, trichloride, thionyl chloride and the like, or Demotrichloride, antimony pentachloride andarsenic pentachloride, In the Py-C-halogenanthrapyrimidines thus obtained the halogen atom can readily be replaced by organic radicals either directly by condensation with amino or hydroxy compounds, or by way of the corresponding diazo compounds which may be obtained from the amines prep red from the halogen compounds by heating them with ammonia. diazo compounds other substituents, such as mercapto, cyano and like substituents, can readily be introduced into the Py-C position of the anthrapyrimidines.

The preparation of the acylaminoanthrapyrim idines by condensation of aminoanthrapyrimidines with organic acids, anhydrides or, halides, or halogenanthrapyrimidines with acid amides, and the corresponding, condensation of the aminoanthraquinones or halogenanthraquinones with organic acids, anhydrides or halides, or acid amides, before the formation of the pyrimidine ring, is best carried out in 'an, inert organic solvent or diluent, in particular aromatic solvent or diluent of high boiling point, for example nitrobenzene, halogenbenzenes, nitro-and halogen derivatives of homologues of benzene, naphthalene and its halogenderivatives and the like. The condensation is best carried out at, temper atures above 100 C. and may be accelerated by the addition of condensing catalysts, such as metal and metal compounds, for example copper and iron, their oxides and salts thereof, such as their acetates and carbonates. Acid binding agents are also preferably added, for example pyridine, quin- By 'way of the oline, tertiary organic bases, such as dimethylaniline, sodium and potassium carbonates, acetates and phosphates. The formation ,of the pyrimidine ring when starting from anthraquinones can be carried out in the absence as well as in the presence of indifferent diluents, for example phenol, nitrobenzene, trichlorbenzene or .in the case of anthraquinone-l(N).2-oxazoles water or alcohol may be used as diluents. Agents which accelerate reaction, for example anhydrous boric oxide, oxalic acid, potash, zinc chloride copper 5 and its salts, may be added. Therea'ction prodnets are usually obtained in good yields and in a crystalline form. If necessary they may be purified by the usual methods, as for example by' crystallization or treatment with" oxidizing agents, for example in the form of their aqueous pastes with hypochlorite solution. They dissolve inconcentrated sulphuric acid,. usually to give a yellow to orange coloration. They are comparatively difiicultly soluble in the usual organic solvents and, contrasted with the anthrapyridones and anthrapyrimidones, are insoluble in alkalies. With alkaline hydrosulphite solutions they usually yield violet brown vat solutions from which vegetable, animal and artificial fibres are usually dyed greenish yellow to violet shades.

The shades produced with the acylaminoanthrapyrimidines prepared in the aforesaid man ner may be varied by halogenation.

The halogenation may be carried out by a variety of methods, as for example in inorganic or organic media, such as sulphuric acid and its derivatives, for example chlorsulphonic, and alkylsulphonic acids, water, nitrobenzene, chlorbenzene and the like, or in the absence of diluents, or in the presence of halogen transferrers, as for example iodine, sulphur, iodine chloride, selenium, dimethylaniline, antimony, iron, iron chloride and aluminium chloride. The reaction products are usually obtained in good yields and in a good state of purity; when necessary they may be purified by the usual methods, as for example by crystallization, by boiling with organic solvents or by treatment with alkali metal hypochlorites or other oxidizing agents. The halogenacylaminoanthrapyrimidines differ from the initial materials free from or poor in halogen usually as regards shade of color and are in part superior thereto as regards fastness to washing and chlorine. Thus for example, from S-benzoylamino-1.9-anthrapyrimidine (which gives yellow dyeings) a clear orange is obtained by chlorination and from the acylamine derived from 4-amino-1.9-anthrapyrimidine and diphenyl-4-carboxylic acid (which gives greenish yellow dyeings) a halogenation product which gives clear greenish yellow dyeings is obtained by treatment with bromine or sulphuryl chloride, the said product being completely fast to chlorine in contrast to the initial material and superior to the latter as regards fastness to washing, kier boiling and light.

The following examples will further illustrate the nature of this invention but the invention is not restricted to these examples. The parts are by weight.

Example 1 36 parts of 1-amino-4-benzoylaminoanthraquinone are heated to from 180 to 185 C. with 125 parts of formamide for 8 hours while stirring. After cooling the reaction product is filtered by suction, washed with alcohol and dried. The reaction product obtained in the form of yellow needles in good yields dissolves in concentrated sulphuric acid giving an orange coloration. It crystallizes from nitrobenzene, if necessary with the addition of a little benzoyl chloride, in the form of green yellow needles. The 4-benzoylamino-LQ-anthrapyrimidine with alkaline hydrosulphite yields a violet brown vat solution from which cotton is dyed powerful clear green yellow shades of very good fastness. A brown ammoniacal vat yields powerful brilliant green yellow shades on wool.

The reaction may also be carried out in the presence of diluents, as for example phenol. The product is identical with the reaction product obtainable from 4-amino-l.9-anthrapyrimidine (obtainable by boiling IA-diaminoanthraquinone with. benzoyl. chloride.

with formamide in phenol) A reaction product of similar color is likewise obtained from 4-chlor-1.9-anthrapyrimidine by heating with benzamide.

Example 2 I 5 parts of 4-amino-1.9-anthrapyrimidine are suspended in parts of nitrobenzene. After adding 6 parts of'l-aminoanthraquinone-2-carboxylic acid chloride, the whole is heated to C. for several hours while stirring, then for a short time at C. and then for from 1 to 2 hours at the boiling point. The whole is allowed to cool and the reaction product which separates in the form of yellow red needles is filtered off by suction. The yield is almost theoretical. The product dissolves in concentrated sulphuric acid giving an orange coloration, yields a dark brown vat and dyes cotton red shades having very good fastness.

The corresponding acylamine from 4-amino- 1.9-anthrapyrimidine and anthraquinone-2-carboxylic acid dyes green yellow shades as does that with pyrazolanthrone-Z-carboxylic acid and also the meta-methoxy4-benzoylamino derivative.

Example 3 1 part of 1-amino-5-benzoylaminoanthraquinone, 2 parts of formamide and 4 parts of phenol are boiled for several hours while stirring. When the solution has become orange yellow in color, it is allowed to cool, diluted with from 6 to 7 parts of ethyl alcohol, allowed to cool and the reaction product which separates in a crystalline form is filtered off by suction. It crystallizes from nitrobenzene, preferably with an addition of a little benzoyl chloride, in the form of yellowish needles of 5 benzoylamino 1.9 anthrapyrimidine. It dissolves in concentrated sulphuric acid giving an orange coloration and yields clear yellow dyeings of good fastness from a brown vat.

Example 4 In the same manner 5-ethyl and 5propylamino-1.9anthrapyrimidine which are obtainable from 5-chlor-1.9-anthrapyrimidine by means of ethyl or propylamine, may be subjected to acylaion.

Similar reaction products are obtained in an analogous manner by starting fromv alkylation products of aminoanthrapyrimidines obtained in sulphuric acid by means of alcohols.

Example 5 5 parts of 4-amino1.9-anthrapyrimidine in 50 parts of ortho-dichlo-rbenzene are heated to boiling, after the addition of 10 parts of parachlorbenzoyl chloride, and the whole is boiled until there is no further lightening in color, which is usually the case after a few hours. The whole is then' allowed to cool and the reaction product-which separates in a theoretical yieldin the form of lustrous crystal spangies lsfiltered 7 off by suction. 'It dissolvesin sulphuric acid 'yield green yellow dyeings .are likewise obtained in quantitative yields from 4-amino-1.9-anthrapyrimidine and ortho-chlorbenzoyl chloride or 2.4-dichlorbenzoy1 chloride. 7 V

The corresponding condensation product from 5-amino-1.9-anthrapyrimidine and ortho-chlorbenzoyl chloride gives reddish yellow dyeings.

-Tre acylamine obtainable from anthrapyrlm- .idine by nitration by means of nitric acid in sulphuric acid, reduction of the nitro compound to the amine and treatment of the amino compound with para-chlorbenzoyl chloride dyes cotton yellow shades.

. 7 Example 6' 247 parts of 4-amino-1.9-anthrapyrimidine in 2000 parts of ortho-dichlorbenzene are heated slowly while stirring after the addition of 5 00 parts of meta-methoxybenzcyl chloride, and then boiled for a short time. The reaction product which separates in a crystalline form in excellent yields is filtered ofi by suction an may be crystallized from trichlorbenzene. It dissolves in concentrated sulphuric acid giving an orange coloration, and gives a violet red brown vat from which cotton is dyed powerful green yellow clear shades of very good fastness.

The condensation product with beta-naphthoyl V chloride (yellow needles) also dyes cotton greenish yellow shades from a red brown vat. The acylamine from 2 molecular proportions of 4- aminoanthrapyrimidine and 1 molecular proportion of isoterephthaloyl chloride also gives yellow dyeings. Example 7 2 parts of 4-amino-1.9-anthrapyrimidine in 40 parts of trichlorbenzene are heated to boiling for several hours while stirring after the addition of 10 parts of acetic anhydride. The whole is then allowed to cool and is worked up in the usual manner. The'acetyl derivative obtained forms yellow crystals, dissolves in concentrated sulphuric acid giving a golden yellow coloration and yields comparatively pale green yellow dyeings on cotton and wool from an orange vat.

A green yellow reaction product the acetyl-pchlorbenzoyl-amino derivative, is obtained therefrom by treatment with para-chlorbenzoyl chloride. It dissolves in concentrated sulphuric acid giving a golden yellow solution, and furnishes .a brown-violet vat.

The product from 4-amino-1.9 -anthrapyrimidine and oxalyl chloride is a green yellow crystalline powder which is very difiicultly soluble.

The reaction product of the above amino compound with chlorcarbonic acid ethyl ester is also yellow as is also the reaction product with phosgene or thiophosgeiie or perchlormethyl mer captan. i Example 8 65 parts of 2-amino-C-phenyl-LQ-anthrapyrimidine (obtainable from C-phenylanthraquinone-2.1-oxazo1e by treatment with ammonia according to the following formulae:

can 7 The reaction proceeds according to the following formulae:

(1013s 7 o t i A -NH1 oioo- 5 l| I N H A N.0C

2 benzoylamin'o-C phenyl 1 9 -anthrapyrimi-. dine forms yellow needles and dissolves in concentrated sulphuric acid giving a golden yellow coloration. e

The reaction product of anthraquinOne-Z- carboxylicacid chloride on amino-1.9.4.10-anthradipyrimidine (obtainable from 1.9.4.10-anthradipyrimidine (obtainable from l-.5 diaminoanthraquinone) by nitration by means of a mixture of nitric and sulphuric acids and reduction of the nitro compound) is alsoa yellow crystalline powder which dissolves in concentrated sulphuric acid giving an orange coloration.

2-benzoylamino 1.9-anthrapyrimidine and 2- anthraquinonebetacarboxylamino- 1 9 -anthrapyrimidine (obtainable from' .anthraquinone-2.1- oxazole by'treatment with ammonia and conversion of the Z-amino-l.Q-anthrapyrimidine formed with Z-anthraquinonecarboxylic acid chloride) yield pale yellow dyeings on'cot'ton from orange brown vats.

Example 9 30 parts of chlor-4-amino-1.9-anthrapyriniidine (prepared from 4-arnino-LQ-anthrapyrimidine by treatment with chlorine in chlorsulphonic acidm thepresence of iodine-andsulnhur as boiled for a short time in transferrers) in 500 parts of naphthalene are heated to boiling, after the addition of 100 parts of benzamide, 60 parts of potash and 3 parts of copper oxide, while stirring until there is no further formation of dyestuffp The whole is then allowed to cool and is worked up in the usual manner. The resulting reaction product is an olive yellow powder, dissolves in concentrated sulphuric acid giving an orange coloration and dyes cotton yellow from a violet brown vat.

By treating the reaction product with parachlor-benzoyl chloride, a benzoylamino-parachlorbenzoylamino-LQ-anthrapyrimidine giving yellow dyeings is obtained.

Example 10 247 parts of 4-amino-1.Q-anthrapyrimidine are boiled for a short time in 2500 parts of nitrobenzene with 220 parts of orthotoluylchloride while stirring. The mass is allowed to cool and filtered by suction. The resulting reaction product which is a crystalline yellow powder dissolves in concentrated sulphuric acid to give an orange solution, furnishes a dark violet brown vat and crystallizes from organic solvents of high boiling point in the form of yellow needles. From the vat it dyes animal and brilliant greenish yellow shades of excellent fastness to washing and boiling.

In an analogous manner similar reaction products which mostly dye yellow shades are obtained from l-amino-l.Q-anthrapyrimidine and other carboxylic acids, for example the para-cyanbenzoyl-l-amino-l.Q-anthrapyrimidine, the para-fluorobenzoyl-l-amino-1.9-anthrapyrimidine (yellow needles), para-methoxybenzoyl-4-amino-1.9-

anthrapyrimidine and the corresponding methoxy derivative, meta-methylbenzoyl-4-amino-1.9- anthrapyrimidine, 3.4-dichlorobenzoyl-4-amino- 1.9-anthrapyrimidine and the corresponding 2.5- and 2.3-dichloro derivatives, 3.4.5-trichlorobenzoyl-4-amino-1.9-anthrapyrimidine, and also the corresponding cinnamoyl derivative.

Example 11 125 parts of 4-amino-1.9-anthrapyrimidine are 1250 parts of nitrobenzene with 125 parts of para-nitrobenzoylchloride while stirring. The reaction product is filtered off by suction after cooling. It is obtained in the form of yellow needles and in .a nearly quantitative yield. It dissolves in concentrated sulphuric acid giving an orange solution and dyes cotton strong yellowish brown shades from a dark brownish violet vat.

The para-methyl-meta-nitrobenzoyl derivative prepared in an analogous manner is in the form of yellow needles. It dyes strong clear yellow shades. Meta-nitrobenzoyl-4-amino-1.Q-anthrapyrimidine dyes orange yellow shades.

Example 12 250 parts of 4-amino-1.9-anthrapyrimidine are boiled in 3000 parts of nitrobenzene with 145 parts of diphenyl-para-para-di-carboxylic acid chloride while stirring, until no more dyestuff is formed. The mass is allowed to cool and worked up in the usual manner. The reaction product of which an excellent yield is obtained, is in the form of yellow needles, dissolves in concentrated sulphuric acid giving an orange solution and yes cotton yellow shades of excellent fastness from a dark violet vat. The crude product may be purifled by treating an aqueous paste thereof with aqueous sodium hypochlorite solution.

The corresponding derivative of benzophenonevegetable fibres strong para-para'-dicarboxylic acid obtained in "an analogous manner is in the form of yellow needles and dyes cotton greenish yellow shades from 'a brownish violet vat. Similar shades are obtained from the corresponding derivatives of diphenylmono-carboxylic acid or of naphthalene-1.4-dicarboxylic acid or naphthalene-1.5-dicarboxylic acid or of diphenyl-ether carboxylic acids, or of diphenylsulphide or phenylsulphide carboxylicacids.

Example 3 360 parts of para-aminobenzoyl-4-amino-1.9- anthrapyrimidine (obtainable by reducing the para-nitrobenzoyl-l-amino-l.Q-anthrapyrimidine described in Example 11) are boiled for a short time in 3000 parts of nitrobenzene with 170 parts of benzoyl chloride while stirring. The reaction product is filtered off by suction after cooling. The resulting (para-benzoylamino-benzoyl) lamino-1.9-anthrapyrimidine which is obtained with a very good yield and in a state of high purity, crystallizes in yellow needles which dissolve in concentrated sulphuric acid giving an orange solution and dye cotton powerful clear yellow shades of excellent fastness from a warm violet brown vat. 1

Reaction products dyeing similar shades are obtained by employing,instead of benzoyl chloride, in an analogous manner para-chlorobenzoylchloride or 2.5-dichlorbenzoyl chloride or oxalyl chloride or meta-methoxybenzoyl chloride.

The acylamine obtained from para-aminobenzoyl 4 amino 1.9 anthrapyrimidine and anthraquinone-beta-carboxylic acid in an analogous manner dyes yellow shades. Use may also be made of carboxylic acids having a still higher molecular weight, as for example carboxylic acids derived from thiazolanthrone, benzanthrone or anthraquinone thioxanthone. from anthrapyrimidine, as .for example 1.9- anthrapyrimidine-2-carboxylic acid (obtainable from 1-aminoanthraquinone-2-carboxylicv ethyl ester and formamide and saponification of the resulting anthrapyrimidine -2- carboxylic ester melting above 360 C.) may also be employed.

Example 14 It crystallizes in yellow needles and dyes cotton clear greenish yellow shades of excellent fastness from a brownish violet vat.

Example 15 24.? parts of '7.-amino-LQ-anthrapyrimidine (obtainable by the reaction of formamlde on 1- aminoanthraquinone-l-sulphuric acid and replacing the sulphuric acid group by the amino group) are heated for a short time to boiling while stirring in 250 parts nitrobenzene with parts of benzoyl chloride, the reaction mixture then being worked up as usual. The reaction product obtained in the form of yellow needles yields green yellow dyeings of very good fastness, in particular against washing, on cotton from a dark violet brown vat.

The acyl compound obtained in an analogous manner from 4-amino-LQ-anthrapyrimidine and para-brombenzoic acid dyes strong brilliant Carboxylic acids igreenish yellow :shades. tYellow' dyeings are also obtained b y the productsproduced from paraiodbenzoyl chloride or brom-l-naphthoyl chloride (obtainable by brominating unaphthoici'acid -in glacial acetic acid and heating the product with:.thionyl chloride) and 4-amino-L9-anthra- :pyrimidine. Yellow orange orred shades arepro- .duced by the acyl compounds produced from '4- famino-1.9-anthrapyrimidine and'the chlorides of V sebacic, adipic, stearic, pyroracemic, hexahydrobenzoic, benzanthrone 2 carboxylic, anthra -Quinone-l-carboxylic, salicylic, cresotinic, 2.4.5-

vtrichlorbenzoic, "cliphe'nyl carboxylic, diphenyl- 'Tniethane'carboxyli'c, anthanthrone carboxylic and 15 fallo ms -.naphthodianthrone ,The acyl co'mpound'of thesaid anthrapyrimidine Land -Z-aminQanthraquinone 3 carboxylic acid chloride dyes brown shades. lactionproduct is obtained from lmolecular proportion of: phosgene, 1 molecular proportion of .fl aminoanthraquinone and 1 molecular proporcarboxylic acid.

A yellow dyeing retion of 4-amino-LQ-anthrapyrimidine.. .YIristead of 7.-amin-1.9-anthrapyrimidine mentioned in the first paragraph of this example its substitution products, for example its halogen and methyl derivatives can be subjected to benzoylation, the products obtained likewise dye yellow shades.

Example 16 250 partsof S-amino-LQ-anthrapyrimidine Vareheated to boiling for ashort time in 5000 parts of .nitrobenzene with .110 parts of isophthaloylchloride. The yellow crystalline reaction product obtained by filtration of. the reaction mixture dissolves in concentrated sulphuric acid to give an-orange red solution and. crystallizes .from organic solvents of high boiling point. .It

dyes c0tton strong golden yellow shades of very goodfastness from a red vat having a violet tinge.

Dyestufi'sfurnishing similar shades and having similar properties are obtained by the use of terephthaloyl chloride or the mixture of isoand terephthaloyl chloride. .Dyestufls dyeing 'more greenish yellowshades are obtained by employing suecinic, adipic or sebacic acid chloride as acylating agent. Theacylamino derivatives obtained by means of diphenyl .p.pr-.dicarboxylic and benzophenoner-pp-dicarboxylic'acid chloride ,dye" cotton orange or golden yellow shades.

Example 17 .250 parts of -amino-LQ-anthrapyrimidine are heated while stirring for a short time to'boiling in 4000,1parts ,of nitrobenzene with 260 parts of para brombenzoyl chloride. The reaction product, para-brombenzoyl-fi-amino-1.9-anthrapyrimidine, obtained by'filtration of the reaction .mixture after cooling and working up as usual, icrystallizes from trichlorbenzene in small yellow needles dissolvingin concentrated sulphuric acid to a red solution. good fastness are-obtained with the said product Jfroml a red .vat with a violet tinge.

Greenish yellow dyeings of 'Similar dyeings are obtained from paraiodbenzoyl-5eamino-l.Q-anthrapyrimidine, paracyanbenzoyl '5 amino- 1.9-anthrapyrimidine the 1 'ortho chlorb'enzoyl 5 amino 1.9 anthrapy- ILQ-anthrapyrimi'dine.

rimi'dine and the meta chlorbenzoyl-S-amino- Slightly more greenish shades furnishthe 2'.4-dichlorbenzoyl, the 3'.4- dichlorbenzoyl and in particular the 2'.5'.-di-

chlorbenzoyl -"5 amino 1.9 'anthrapyrimidine. "The "para' methylbenzoyl and ,B-naphthoyl-5- heated to boiling for a .acids substituted inthe 4' "amino 119 anthrapyrlmidi'nesfurnishi orang'e dyeings. The para-phenylbenzoylamine derivative dyes strong reddish yellow shades.

' Example 18 parts of 5-amino-LQ-anthrapyrimidine are short time in 500 parts'of nitrobenzene with parts of anthraquinon-Z- carboxylic acid chloride. worked up in'the usual manner is a yellow crys-' talline powder dissolving in concentrated sulphuric acid to give a red solution and dyes cotton clear yellow shades from a brown red vat.

A product dyeing more greenish yellow shades is obtained by the use of 1-chloranthraquinone-2- carboxylic acid chloride instead of anthraquinone-2-carboxylic acid chloride, ;whereas the acylamino compound dyes clear strong red brown shades.

Example 19 24.7 parts ofe-aniino-LQ -anthrapyrimidine are heated to boiling in 250 parts of orthodichlorbenzene after the addition of parts of 4'- bromdiphenyl-4-carboxylic acid chloride until a sample of the reaction product melts at about.

310 C. The reaction mixture is then Worked up as usual. Thedyestufi thus obtained dyes the vegetable fibre from a brown violet vat strong greenish yellow shades.

Similar dyeings are obtained from the acyl-,-

amines of 4-amino-1.Q-anthrapyrimidine produced by means of other diphenyl-4-carboxylic the 4'-ethyl, -4-.chloro and 4'-benzoyl derivatives.

The acylamine produced by the action of parachlorbenzoyl chloride on the anthrapyrimidine produced from 1.4-diamino-p-methoxy anthraquinone with formamide, dyes thevegetable fibre yellow shades which are also obtained by means of the acylamine produced manner from 'para-chlorbenzoyl chlorlde and' the LQ-anthrapyrimidine derivative produced from lA-diamino 2 bromanthraquinone or 1.4;- diamino 2 methylanthraquinone and formamide.

The anthrapyrimidine derivative produced from 1.4 diamino 5 nitroanthraquinone and formamide furnishes on condensationwith benzoyl chloride a dyestuff dyeing reddish ye llow'shades. The dyestuffs obtainable from 5-amino-L4-dibenzoyldiaminoanthraquinone and formami'de furnishes rose red shades.

Example 20 15 parts of 1-amino-8-benzoylaminoanthraquinone (obtainable by partial benzoylation of 1.8-diaminoanthraquinone) are heated to boiling for several hours with 30 parts of formamide in parts of phenol While distilling 011 the water formed. "When the reaction mixture has become yellow, it is allowed to cool and the 8-benzoylamino-1.9-anthrapyrimidine formed filtered off. It is a powder crystallizing from high boiling'solvents in yellow needles, dissolves in concentrated sulphuric acid to give a golden yellow solution and The reaction product produced by means of -1- aminoanthraquinone -'2-carboxylic acid chloride in an analogous P sition, for example 7 dyes cotton yellow shades from a brown violet.

vat.

In an analogous manner the (2'.5-dichlorbenzoyl)-5-amino-1.9-anthrapyrimidine from 1- amino (2'.5' dichlorbenzoyl) -5'- amino'an thraquinone, the (para-chlorbenzoyl) -4-amino- 1.9-anthrapyrimidine from l-amino-(para-chlorbenzoyl) -4aminoanthraquinone, the (benzanthraquinone 6' carboxyl) 5 amino 1.9 anthrapyrimidine from l-amino-(benzanthraquinone-6' -carboxyl) -5-aminoanthraquinone is obtained. The (dichloranthraquinone 2.1 benzacridone- 3' carboxyl) 4 amino 1.9 anthrapyrimidine is obtained by partial acylation by means of benzoic acid anhydride of the acylamine prepared from 1.4-diaminoanthraquinone and dichloranthraquinone-2.1-benzacridone-3'- carboxylic acid.

The 4-benzoylamino-2-amino C phenyl-1.9- anthrapyrimidine is obtained by heating 4-benzoylamino-C-phenyl-Z.l-oxazol with ammonia.

Example 21 26.2 parts of 2-amino-C-methyl-1.Q-anthrapyrimidine (obtained by heating anthraquinone- C-methyl2.1-oxazol with ammonia) are heated to boiling for a short time in 200 parts of nitro benzene with 30 parts of anthraquinone-2-carboxylic acid chloride. The reaction proceeds according to the following formulae:

1.9-anthrapyrimidine dyeing strong clear greenish yellow shades from a violet vat is obtained by heating 4-amino-L9-anthrapyrimidine and diphenyl-4-carboxylic acid chloride in a mixture of nitrobenzene and pyridine. The acylamines prepared in an analogous manner from 4-amino- 1.9-anthrapyrimidine and 4-nitrodiphenyl-4- carboxylic acid (obtainable by nitration of diphenyl-para-carboxylic acid by means of nitric acid in crude chloroacetic acid) or dichlordipheny1-4-carboxylic acid (obtainable by chlorinating diphenylcarboxylic acid in trichlorbenzene with chlorine in the presence of iodine at between and C.) or with quinoline-6- carboxylic acid likewise dye yellow shades.

The reaction products may be isolated by distilling off the diluent, if desired under reduced pressure or by means of steam, or by means of steam under reduced pressure. They are readily soluble in some diluents miscible with water, such as chloroacetic acid, and can be reprecipitated from such solutions by dilution with water.

f i a if N O a AO/NH, (D G 0 O O H01 Y Y Y After completion of the reaction which may be recognized by the evolution of hydrogen chloride ceasing, the reaction mixture is Worked up as usual. The acylamine obtained in yellow needles issolves in concentrated sulphuric acid to give a yellow solution and dyes the vegetable fibre yellow shades from a violet brown vat.

The 2 benzoylamino C methyl 1.9 an thrapyrimidine as well as the C-ethyl and the C-propyl derivative likewise dye yellow shades.

The para chlorbenzoyl 4 amino C phenyl-LQ-anthrapyrimidine (obtainable by heating 4 amino C pheny 1.9 anthrapyrimidine with para-chlorbenzoyl chloride) dyes cotton reddish yellow shades from a violet vat. The C-naphthyl and the C-para-chlorphenyl derivative dye similar shades as do also the isomeric acylamines of the 5-amino-1.9-anthrapyrimidine series.

Example 22 247 parts of of amino-1.9-anthrapyrimidine are heated to boiling while thoroughly stirring in 1000 parts of nitrobenzene after the addition of 240 parts of crude pyridine and 190 parts of parachlorbenzoylchloride, the mixture being kept at the said temperature until the separation of dyestufi does not anymore increase. The mixture is then allowed to cool and the reaction product separated in the form of pure yellow needles filtered off. theory. The dyestuff is practically identical with the product described in Example 5.

Pyridine alone may also be employed as diluent instead of the mixture thereof with nitrobenzene.

The yield is about that required by.

In order to increase the property of printing of the dyestuffs they may be mixed. intimately with glycerine or other additions improving the property of printing such as anthrafiavinic acid or mixtures of such additions.

Example 23 36 parts of 4-chlor-Z-methyl-C-phenyl-1.9- anthrapyrimidine (obtainable by diazotizing 4- amino 2 methyl C phenyl 1.9 anthra pyrimidine and replacing the diazo group by chlorine) are heated at about C. for about 2 hours in 100 parts of nitrobenzene after the addition of 5 parts of potash, 1 part of copper acetate and 50 parts of para-toluene sulphamide and then heated for several hours at about C. After cooling, the 2-methyl4para-toluene sulphamide C phenyl 1.9 anthrapyrimidine is filtered oil. It is a yellow crystalline powder, dissolves in concentrated sulphuric acid to give a brown violet solution and dyes cotton yellow shades from a brown violet vat.

The 4 para toluenesulphamide 2 methyl 1.9-anthrapyrimidine obtained in an analogous manner dyes greenish yellow shades.

Example 24 20 parts of 5-amino-4'-benzoylamido-1.1- anthrimidecarbazol (obtainable by partial saponification by means of sulphuric acid at between 35 and 50 C. of 5.4-dibenzoyldiaminol.l-anthrimidecarbazol) are heated to boiling for :severalhours with 100 parts of formamide in 200 parts of phenol. The reactionproceeds .according to the formulae:

fast to chlorine, the. reaction mixture is allowed to cool and the '4-benzoylamino-5.IO-pyrimidino- 1.1-anthrimidecarbazol formed filtered off. It is a brown crystalline powder, dissolvesin concentrated sulphuric acid to give a red solution and dyes cotton from a brown vat strong yel-' low brown shades of very good fastness.

w A brown dyeing benzoylaminoanthrapyrimidine derivative is obtained in'an analogous manner from 5-amino-4-benzoylamino8-methoxy- '1.1'-a'nthrimidecarbazol (obtained from 5.4'-dibenzoyl-diamino-8-methoxy-1.1'-anthrimidecarbazol in a manner analogous to that described in the foregoing paragraph.

The reaction product obtained in an analogous manner from 5-amino-5'-benzoylamino-1.1'anthrimidecarbazol dyes golden orange shades.

By 7 condensation of a-aminoacylaminoanthrimides with'formamide in an analogous manner the acylaminopyrimidinoanthrimides are obtained, as are also obtained the benzoylaminopyrimidinoanthrapyrimidines by the action of formamide on a-aminobenzoylaminopyrimidinoanthraquinones. V

In the same manner by the action of formamide on other a-aminoacylaminoanthraquinone derivatives, such as the a-aminoacylamino derivatives of benzanthraquinone, dianthraquinonyls, anthraquinoneacridones, phthaloyl carbazol or other carbazols containing the anthraquinone nucleus for example anthraquinonethioazols and the anthraquinoneazines, corresponding acylaminopyrimidine derivatives are obtained.

Example 25 parts of 5-amino-1.9-anthrapyrimidine are heated for a short time while stirringat between and C. in 500 parts of 2.5-dichlorbenzoylchloride. As soon as the reaction mixture has become pure yellow in color, it is allowed to cool and the excess of dichlorbenzoylchloride filtered ofi". 'The 2'5'-dichlorbenzoyl-5-amino- 1.9-anthrapyrimidine is identical with the product described in Example '17.

The 5-acetylamino-1.9-anthrapyrimidine is obtained in an analogous manner by heating 5- amino-1.9-anthrapyrimidine in :acetic acid anhydride, as is obtained the phenylacetyl-5.-amino LQ-anthrapyrimidine by the action of phenyl .acetic acid "chloride.

.Eammple 2ft :areheatedto boiling while stirring in 200 parts of-nitrobenzene with-35 parts of 4"-bromdiphenylfI-CELI'bOXYllC acid chloride (obtainable by brominating diphenyl-i-carboxylic acid and treating the product with phosphorus pentachloride). When the reaction mixture has become yellow orange, it is allowed to cool and the (.4-bromdiphenyl-4carboxyl) -5-a .mino- 1.9 dine separated in yellow needles filtered off. It dyes cotton golden orange :shades of very good fastness against washingand boiling with soda. 'I'he same product is also obtained .by the action of formamide on 5-amino-(4'-bromdiphenyl-4- carboxyl)1-aminoanthraquinone. In-an analogous manner the acylamines of aminoanthrapyrimidines and 4-, 5-, and 8-aminoanthraquinonel-carboxylic acids can be prepared. The latter aminoanthraquinonecarboxylic acids can be ob-' tained by treating the corresponding chloroaminoanthraquinones or chlorbenzoylaminoanthraquinones with cuprous cyanide and subsequent saponification.

-anthrapyrimi- Example 27 .18 parts of (1'-benzene-4-carboxylic acidtion of 12 parts of ll-amino-LQ-anthrapyrimij dine and allowed to cool after the evolution of hydrogen chloride .has ceased. The reaction .product recovered-in the usual manner dissolves in concentrated sulphuric acid to give a yellow solution and dyescotton red orange shades of good fastness from a brown violet vat. Instead of para-aminobenzoic acid other carboxylic acids of aromatic. amines may be used for the preparation of' the acylating component such as aminoanthraquinonecarboxylic acids or pyrimidinoanthraquinone carboxylic acids.

Example 28 10 parts of 5-aminoanthraquinone-2.1'-carbaminoanthraquinone (obtainable by acylating a-aminoanthraquinone with 5-nitroanthraquinone-2-carboxylic acid and reducing the acylation product) are heated to boiling for several hours with .1200 partsqof formamide in;400 parts of boiling in 1000 parts of nitrobenzene parts of para-chlorbcnzoylchloride until the phenol. The reacti n proceeds according to the following formula:

The reaction mixture is then diluted with ethyl alcohol and worked up as usual. product, the 5.10-anthrapyrimidine, is a brown yellow powder which is difficultly soluble and may be purified by means of oxidizing agents, for. example by means of an alkali'metal hypochlorite. .It dissolves in concentrated sulphuric acid to give an' olive yellow solution and furnishes yellow dyeings on'cotton from a brown violet vat.

The reaction may also be carried out in trichlorbenzene or nitrobenzene'. An addition of boric oxide, zinc chloride'or copper salts accelerates the reaction. Similar reaction products are, obtained in an analogous manner by treating acylamines of other m-aminoanthraquinone carboxylic acids with formamide; In the same manner m-aminoacylaminopyrimidinoanthraquinone may be converted by means of formamide into acylaminopyridinoanthrapyrimidines.

Example 29 parts of '3-amino-l.Q-anthrapyrimidine (obtainable by condensation of 1.3-diarr'1inoanthraquinone with formamide) ar'eheated to coloration of the reaction mixture has become olive yellow. After cooling, the reaction product separated in crystalline form is filtered off. It

dissolves in concentrated sulphuric acid to give a golden yellow solution and dyes cotton yellow shades from a brown Vat. The reaction product obtained by acylation of 'G-amino-lLQ-anthrapyrimidine by means ofpara-chlorbenzoylchloride dyes yellow shades. a r r a "The-product obtained by acylation of diamino 1.9 anthrapyrimidine (prepared by' co'ndensing the dichlo'ranthrapyrimidine,'produced by chlorinating B-chlQr-anthrapyrimidine in trichlorbenzene in the'presence of iodine, with ;para-- toluene sulphamide and saponification by means of sulphuric acid) by means ofbenzoyl chloride dyes orange shades. The product obtained by acylating by means of l-aminoanthraquinone 2 'carboxylic acid chloride the polyamino-l.9.5 .10-

anthradipyrimidine (obtainable by chlorinating 1.9.5.l0-anthradipyrimidine which may be produced-by acting on with formamide, condensing the chlorination product with para-toluene 'sulphamide and saponifying the condensation product by means of sulphuric acid) dyes brown shades.

H 7 Example -30 325-parts ofbromo-5-a1nino-LQ-anthrapyrimi- The reaction l-anthraquinone-Z-carbaminm with 3 anthraquinone-l-sulpho chloride.

"1 .5-diaminoanthraquinone stirring,

9 diiieYobtainable by brominati ng 5-amino-L9-an thrapyrimidine in chlorsulphonic acid) are heated to boiling for a short time in 3000 parts of nitrobenzene with 220 parts of 2.5-dichlorbenzoy1 chloride after the addition of 100 parts of calcined soda. After cooling the reaction mixture is, worked up as usual. The dyestufi obtained dissolves in concentrated sulphuric acid to give a golden yellow solution and furnishes yellow dyeings of a very good fastness from a brown violet vat.. r The 5-benzoylamino B naphthoylamino-1.9-

anthrapyrimidine is obtained in an analogous manner by the action of fl-naphthoyl chloride on amino- 5 -'benzoylamino 1.9 anthrapyrimidine which may be prepared by condensing the aforesaid brom-5-aminoanthrapyrimidine with paratoluene sulphamide, benzoylating the product thus obtained and partially saponifying the latter product. a

A similar reaction product is also obtained by treating 1 molecular proportion of the correspending diamino-l.Q-anthrapyrimidine with 1 molecular proportion of benzoyl chloride and 1 molecular proportion of B-naphthoyl chloride. A reaction product is obtained in the form of orange needles dyeing cotton orange shades from a brown violet vatby reaction of parachlorbenzoyl chloride on polychlor-S-amino-LQ-anthrapyrimidine 45 which may be prepared by saponification .by means of sulphuric acid of the chlorination product of 5-benzoylam1no-1.9-anthrapyrimidine;

Example 31 24.? parts of 2-amino-C-phenyl-1.9-anthrapyrimidine are heated to boiling for a short time in 250 parts of nitrobenzene with 30 parts of After cooling the acylation product is filtered off. It is a yellow 55 powder, dyes cotton yellow shades from a brown vat and dissolves in concentrated sulphuric acid to give a golden yellow solution.

A similar reaction product is obtained by the employment of the isomeric anthraquinone-2- 5 sulpho chloride. Yellow dyeing acylation products are obtained in an analogous manner by the action of benzene-, 0-, or p-toluene sulpho chloride on Iamino-l.Q-anthrapyrimidine.

Identical reaction products are obtained by condensation of the corresponding halogen anthrapyrimidines with the corresponding sulphamides.

36.7 parts ,of 4-benzoylamino-L9-anthra- 70 pyrimidone are heated for several hours, while at between and C. in 200 parts of nitrobenzene with 22 parts of phosphorus pentachloride. After completion of 75 concentrated sulphuric acid to give a low solution and dyes cotton strong, clear greenish yellow shades of very good fastn'ess from a brown 1 violet vat.

the ,reaction the reaction 1 1 51 1. 8 usual man e which according to analysis is a C-chlor-4- ben zoylamino-LQ-anthrapyrimidjne, dissolves in mi tureis worke on By the condensation ation product with anew dyestuffs dyeing different shades are-btained.

By treating the -benzoylamino-l.9-anthra- .pyrimidone (obtainable by condensingd-amino- 5-benzoylaminoanthraquinone vvith urea) in the manner described in the first paragraph of this example a dyestuff is' obtained crystallizing in cotton, 2 Y thrapyrimidine is V nor by treating 8-2'15' -dichlorbenzoylaIl 1-inO-1;9-. anthrapyrimidone with and 8-benzoylamino-1.9 anthrapyrimidones pyrimidone 'methylanthraquinone); the 'acylaminoanthrapyyellow needles and furnishing yellow dyeings on jC-jCh-lor-B-Z'fif-dic v v obtained in an analogous manride. It dyes the vegetable fibre yellow shades, from a dark violet vat. e e Substitution products of the aforesaid 5"- be subjected to chlorination in the aforedescribed manne f r xa th 5-be l y aminoli me x ,-9ant ranyr d0ne. the lsi en- (obtainable from amino 1.4 dibenzoyldiamihoan hraqui zoyldiamino-5,lo-anthrapyrin idone 7 none) the 4-benzoylam1n -3-lncthy1-LQ-anthraf l-amin A- enz y a inothe acyl radical, such as nit qb z m n r. a

rimidones substituted in the chlorbenzoylamino kylbenzoylaminm, 'allgoxyben zpylaminog phenyl- V ms-naphthodianthrones. and the V 2 to 3 hour's while leading in hydrobenzoic acid.

benzoylamino-fand jarylaminoanthrapyrimidones.

Ezrample; 33"

20c partsof 5-benzoylamino-l .Q-anthrapyrimi dine in 1000 parts otf trichlcrbenzene are heated to 140 C. after the addition of; 5 parts-oi iodine and are kept atthe said temperature i'or from; chlorine. The re- 7 action mixture is, allowed to cool and, thejreaction product which has separated in. the; form of; orange red crystals is filtered oiI try suction. It; dissolves in concentrated sulphuricacid giving; an orange coloration and dyes vegetable fibres clear,

powerful golden orange shades diver-y good fastness from a brown violet vat. The corresponding chlorination product of 4 benrgoy lamino-l.Q-anthrapyIimidine gives green yellow 'dyein a, t at -anthr quinou rfiecara m qfi-p en .-9 -a t r pyrimidine. gives ep, low dyeings as does benzoyl) -amino-l QFanthrap rimidine.

The reaction. produc golden" yel of the aforesaid chlorine or ,B-aminoanthraquinones phosphorus pentachloa mayi her aci s. m y re obtaina 7 la nle 3 5 parts of, a 10 per cent aqueous paste of the and diphenyl-4. -carboxylic acid, afteran' addition of 30 parts of bromine,

sti -ring. 'When 'a sample I dyeing entirely stable to chlorine (which is usually the case aftera few hours) the excess of bromide is removed by the usual methods and the reaction product containing bromine is filtered off by suction. It dissolves in concentrated sulphuric acid giving an orange coloration and yields greenish yellow clear dyeings of very good fastness on vegetable fibres from a cold or warm. violet blue vat.

Similarly, in a corresponding manner from the isomeric dyestuif from 5-amino-L'Q-anthrapyriinidine' is superior iii-its fastnes's td V with soda to the dyestufl free from bromine.

l f-t mpkfi H V 50 parts or the; initial material employedim paragr h 1 mple 3.4 parts of nitrobenzene." Aft r a n 5 par s'o iodine and '75 parts of sulphuryl. chloride; the. suspension isheated tic-8Q? atthe 'said temperature for from 3 to 4 hours, heated for'from allowed to cool. is filfifii d off by The chlorination s ct n-i I is 'y l w crysta line powder which dissolves in concentrated, 1111.

phuric acid giving an orange coloration and dyes v cotton clear, powerful yellow shades entirely'fast to chlorine and washin'g'from a blue violet vat.

Example 3-6 100 parts of 5-benzoylamino=1.Q-anthrapyrimiin are ntroduced, t om to 5. C- while stirring into. a'suspensionof 100 parts of bromine and 3' parts of iodine in 1000 parts of chlorsulphonic, acid. The whole is, heated to from 20 to hours; the reaction product is then worked up by precipitation in waterand filtration by suc-.

are heated to boiling: on a waterbath under a reflux condenser while withdrawn yields aare Susp nded in 500.

m 2 hours at 9.0: cand then pr duct formed r acylamine from 4-amino-1LQ-anthrapyrimidine the bromination product obtainable '20. washing and boiling C. w l st rr ke tion. The resulting bromination productjyields,

orange dyeings on cotton from a brown violetvat.

Example 37- OI 2-am -1- -anthrapyrimidme are:-

a d boili t r a. s or time in- 2.00.- arts or nitrobenzene with 20 partsot metahmrb z r chloride. he meta-w rbenzoyhz-aminoelizsan hrapyrimi n fo medis. filtered. on? from the, d r act on-mixtu e. I, d ssgl e i c nc ntrated ye lo ol tion and dyes, from a brown vat.

Similar y ein products ob n d y t o an, e va m n or: -dichlQt-. 2.3-dich1or1, 3;;4-dich1 or or trichlorbenzoyl chlo cot on yellow shad s,

ride instea of the. 20 parts. of meta-'chlQrben-zoyl;

r de-1 By h wh n o a os ntoluie acid h r e r ose te p th lq l; ride on. 2-

amino-.LQ-anthrapyrimidine likewi products are obtained dyeing yellow shades.

.What we, claim is: r

1, A process of producingcoloring matters, which V pyrimidine with an organic acylating agent.

2. A process of producing coloring matters, inch mp es: o d sin n.

, terms; yellow needles. su phuric. acid to ive;

comprises condensing an, amlnoanthraa 30 Grand kept at this temperature for about 2 pyrimidine with an organic carboxylic acid chloride.

3. A process of producing coloring matters, which comprises condensing an aminoanthrapyrimidine with an organic carboxylic acid chloride in an inert organic, liquid diluent.

4. A process of producing coloring matters, which comprises condensing an aminoanthrapyrimidine with an organic carboxylic acid chloride above C. in an inert organic, liquid diluent.

5. A process of producing coloring matters, which comprises condensing an aminoanthrapyrimidine with an organic carboxylic acid chloride above 100 C. in an inert organic, liquid diluent in the presence of an acid binding agent.

6. A process of producing coloring matters, which comprises condensing an aminoanthrapyrimidine with an organic carboxylic acid chloride above 100 C. in an inert organic, liquid diluent in the presence of a tertiary base.

'7. A process of producing coloring matters, which comprises condensing an aminoanthrapyrimidine with an organic 'carboxylic acid chloride above 100 C. in an inert organic, liquid diluent in the presence of pyridine.

8. An anthrapyrimidine to which an organic radical is attached by means of an acylamino group which product dissolves in concentrated sulphuric acid to give yellow to red solutions.

9. An anthrapyrimidine to which an organic radical is attached by means of the group Y wherein Y stands for hydrogen or an alkyl group which product dissolves in concentrated sulphuric acid to give yellow to red solutions.

10. An anthrapyrimidine derivative corresponding to the formula:

H I if greenish yellow to violet shades from violet brown vats.

11. An anthrapyrimidine derivative corresponding to the formula:

t if 0 Y in which up to two hydrogen atoms are replaced I by the group in which R stands for the radical of a cyclic compound containing at least one six-membered ring to which may be attached further rings containin which up to two hydrogen atoms are replaced by the group in which R stand for an aromatic radical which product dissolves in concentrated sulphuric acid to give yellow to red solutions and dye the vegetable fibre greenish yellow to violet shades from violet brown vats.

l3. An anthrapyrimidine derivative corre-- sponding to the formula:

in which up to two hydrogen atoms are replaced by the group in which Rstands for a radical of the benzene series, which product dissolves in concentrated sulphuric acid to give yellow to red solutions and dyethevegetable fibre greenish yellow to orange shades from violet brown vats.

l4. An anthrapyrimidine derivative corre- 17. 511 anthrapyrimidine derivative corre sponding to the formula: I sponding to the formulaz 7H r.:' f. t l a r 5:

10 y 1 Y 110 V in which up to two hydrogen atoms are replaced in which upto two hydrogen atoms are replaced y t e. group r by the group. I e 15 NCR n T w e '-'%;C:R

in which R stands for a benzenerradical substiin Which R ta m-chlorbenzene radical 20 uted by a substituent selected from the group Whlch du dissolves concentrated 1.- consisting of halogen, cyano, nitro, alkyl, alkoxy, phurie 9 give yellow t red 501111110115 n phenyl, amino and Substituted amino groups, dye the vegetable fibreigreenish yellow to orange which product dissolves in concentrated sulphuric Shades o Violet br wn Vats- V acid to give yellow to red solutions and dye the l" nei derivative correr 25 vegetable'fibre greenish yellow to orange shades sponding ef u a: a

from violet brown vats. V

15. An anthrapyrimidine derivative corresponding to the formula:

in whi'chup to two hydrogen atoms are replaced bythegroup V 40. 2 "b .v 40

m WhlCh up to two hydrogen atoms are replaced g r I V Y Nc-R I a by the group up e f to a o f in which R stands for a 2.5-dichlorbenzene radi- H cal, which product dissolves in concentrated sul- V H w 7 phuric acid to give yellow to red solutions and in which R stands for a benzene radical 'substldye the vegetable fibre greenish yellow to orange tuted by chlorine, which product dissolves in'con-- shades from violet brown vats.

, centrated sulphuric acid to give yellow to ,red 19. An anthrapyrimidine derivative corre- 0 solutions and dye the vegetable fibre greenish sponding to the formula: l'

yellow to orange shades from violet brown vats. t V V x 16. An anthrapyrimidine derivative corre- (g V sponding to the formula: r

7 V Z N N f V r 55 C\ V Z Z A -Z oz- V :7 r 'e in whichX stands for' hydrogen or an alkyl-group V 0 V i at most two Z s for the acylamino group 7 in which up to two hydrogen atoms are replaced V l V l j by the group 7 V V NC/R N O R in which R stands for an aromatic radical and wherein up to two of the remaining Zs may be 70 halogen, the other Zs being hydrogen, which product dissolves'in concentrated sulphuric acid to give yellow to red solutions and dye the vegein'wh-iclr R stands fora p-chlorben z'ene radical, 'which" product dissolves in concentrated sulphuric acid to'give yellow to red solutions and dye the vegetable fibre greenish yellow to orange table fibre le ye w 00 o a ge shades from a shades from violet brown vats. violet brown vats.

spending to the, iorrnula:

-' '20; An anthrapyrimidine' derivative correspondingto the rormulaz' in which X stands for hydrogen or an alkyl group, at most two Zs for the acylamino group in which R stands for a radical of tlriebenzene series, and wherein up to' two of the remaining Zs may be halogen, the other Zs being hydrogen, which product dissolves in concentrated sulphuric acid to give yellow to red solutions and dye the vegetable fibre greenish yellow to orange shades from violet brown vats. i

21. An anthrapyrimidin sponding to the formulazf derivative correin which R stands for a benzene radical which is substituted by halogen or a cyano group, and wherein up to-two'oi the remaining 21s may be halogen, t he other as being hydrogen in concentrated sulphuric acid to give yellow to red solutions and dye the vegetable fibre-greenish yellow to orange shades from violet brown vats.

22. An anthrapyrimidine derivative correin which X stands for hydrogen or an alkyl group, at most two Zsiiorthe apylamino group in which 'R stands for a benzene radical" substituted by chlorine, and wherein up't'otwo of the remaining :Zs 'may be Lhalogen, the other zs being hydrogen in concentrated sulphuric acid to give yellow to red solutions 'anddye the vegecentrated'sulphuric acid to give yellow to redsotable'fibre greenish yellow to orange shades 'from violet brown vats.

23. An anthrapyrim1dine derivative corresponding to the formula:

in which X stands for hydrogen or an alkyl group, at most two Zs for the'acylamino group --III--CR v H V V in which R stands {for a p-chlorbenzene radical, and wherein up to twoof the remaining Zs may 7 be halogen, the other Zsbeing hydrogen in conlutions' and. dye the vegetable fibre greenish'yel low to orange shades from violet brown vats.

24. An anthrapyrirnidine derivative corresponding to the iormulaz in which X stands for hydrogen or an alkyl group;

at most two Zs for the acylamino group in which X stands for hydrogen or an alkyl group,

at most two Zs for the 'acylamino group I Hi in which R stands for a 2.5 -dichlorbenzene radical, and wherein up to two of the remaining Zs may be halogen, the other Zs being hydrogen in concentrated sulphuric acid to give yellow to red solutions and dye the vegetable f bre greenish yellow to "orange shades from violet brown vats.

1 26.; An anthrapyrimidine derivative corresponding to the formula: i Z

in which a hydrogen atom in one of the alpha? positions is replaced by the acylamino group .1;I. QZR

t a wherein R is .an aromatic radical, which products dissolve in concentrated sulphuric acid to give yellow to red solutions and dye the vegetable fibr re nish yel ow to violet shades from violet brown vats.

27, An anthrapyrimidinederivative corresponding tothe formulas r in which R stands for an aromatic radical, which products dissolve in concentrated sulphuric acid iio give yellow to red solutions. and dye the vegetable fibre greenish yellow'to violet shades 7 'from violet brown vats.

28. 'An anthrapyrimidine derivative corresponding to the formula? 1 E7 a o u-c' -a a in which R stands for a benzene radical which is substituted by halogen or a cyano group, which products dissolve in to give yellow to red solutions and dye the vegetable fibre greenish yellow to orange shades from violet brown vats.

' 29. An anthrapyrimidine derivative corresponding tothe formula:

in which R stands for a benzene radical which is concentrated sulphuric acid 7 substituted by chlorine, which products dissolve in concentrated sulphuric acid to give yellqwtosred solutions and dye the vegetable fibre greenish yellow to orange shades from violet brown vats.

30. The anthrapyrimidine derivative corresponding to the formula:

dissolving in concentrated sulphuric acid'to give a yellow solution and dyeing cotton froma violet brown vat yellow "shades.

=31.- An .authrapyrimidine sponding tocthe to mula:

- derivative correin which R stands 10 a benzene radical Vwhich'is substituted by halogen or a cyano group, dissolving in concentrated sulphuric acid to give a yellow solution and dy ing cotton-1mm a violet brown vat yellow flhades.

32. The anthrapyriinidine derivative 66m:

sponding to the formula:

ci f dissolving in concentrated sulphuric acid to give a yellow solution anddyeing cotton from a violet brown vat yellow shades.

38. An anthrapynmidine derivative corresponding to the for nula:

lit

in which stands for a benzencradicaiwhich is substituted by halogen or a cyano'group, dissolving in concentrated sulphuric acid to. give a yellow solution and dyeing cotton from a violet rown vat ellow shades. v a

34. An anthrapyrimidine derivative corre- 35. The anthrapyrimidine derivative corresponding to the formula: sponding to the formula:

in which R stands for a. benzene radical which dissolving in concentrated sflphuric acid to give 15 is Substituted by chlorine, dissolving in concem a. yellow solution and dyeing cotton from a. violet trated sulphuric acid to give a yellow solution brown vat yellow Shadesand dyeing cotton from a. violet brown vat yel- MAX ALBERT KUNZ. 10w shades. I KARL KOEBERLE. 

